Formation of microcapsules by interfacial cross-linking of emulsifier, and microcapsules produced thereby

ABSTRACT

Pressure-rupturable, oil-containing microcapsules are produced by admixing a water-immiscible, oily material containing an oilsoluble, cross-linking agent, which is either a polyfunctional isocyanate or an orthoester of a group IV element with an aqueous solution of an hydroxyl group-containing, polymeric emulsifying agent selected from the group consisting of polyvinyl alcohol, methyl cellulose, starch and benzyl-substituted starch to crosslink the emulsifier and form a capsule wall at the oil/water interface of the resulting oil-in-water emulsion around the oil droplets. The emulsifying agent is the sole co-reactant for the oil-soluble cross-linking agent.

United States Patent [191 Vassiliades et al.

[ 1 FORMATION OF MICROCAPSULES BY INTERFACIAL CROSS-LINKING OFEMULSIFIER, AND MICROCAPSULES PRODUCED TI-IEREBY [75] Inventors: AnthonyE. Vassiliades, Deerfield;

David N. Vincent, Glenview; Mabrin P. Powell, Chicago. all of III.

{73] Assignee: Champion International Corporation, New York, NY.

122] Filed: Mar. 6, 1972 [21] Appl. No.: 232,183

[52] U.S. Cl. 252/316, 8/79, 71/64 F,

117/362, 117/622, 117/100 A, 264/4, 424/33, 424/35 [51] Int. Cl B0lj13/02, B44d 1/02, B44d 1/44 [58] Field of Search 252/316; 117/100 A, 161KP; 264/4; 260/775 AT; 424/33 {56] References Cited UNITED STATESPATENTS 2.886.445 5/1959 Rosenthal et a1. 99/135 3,242,051 3/1966Hiestand et al. 252/316 X Apr. 1, 1975 3,432,327 3/1969 Kan et al.252/316 X 3,723,372 3/1973 Wakimoto et a1 R24,899 11/1960 Green252/363.5 X

FOREIGN PATENTS OR APPLICATIONS 1,163,023 9/1969 United Kingdom 252/316Primary Examiner-Richard D. Lovering Attorney, Agent, or FirmR0ylance,Abrams, Berdo & Kaul [57] ABSTRACT Pressure-rupturable, oil-containingmicrocapsules are produced by admixing a water-immiscible, oily materialcontaining an oil-soluble, cross-linking agent, which is either apolyfunctional isocyanate or an orthoester of a group IV element with anaqueous solution of an hydroxyl group-containing, polymeric emulsifyingagent selected from the group consisting of polyvinyl alcohol, methylcellulose, starch and benzylsubstituted starch to cross-link theemulsifier and form a capsule wall at the oil/water interface of theresulting oil-in-water emulsion around the oil droplets. The emulsifyingagent is the sole co-reactant for the oilsoluble cross-linking agent.

23 Claims, No Drawings FORMATION OF MICROCAPSULES BY lNTERFACIALCROSS-LINKING OF EMULSIFIER, AND MICROCAPSULES PRODUCED THEREBY Thisimention relates to a microencapsulation system. More particularly, thisinvention relates to a process for the encapsulation of minute oildroplets. to microcapsules produced thereby. and to pressureresponsive.transfer-copy systems employing such microcapsules.

\llicrocapsules containing both liquid and solid nucleus materials havefound widespread acceptance in a variety of commercial applications. Forexample. one of the most widespread uses has been in the artoftransfcr-copy systems wherein minute droplets of a colorless dyeintermediate dispersed or dissolved in an oil are encapsulated andcoated onto a transfer sheet. The dye intermediate is thereaftertransferred to a copy sheet by rupturing said capsules. The underlyingcopy sheet has an adsorbent coating thereon containing a material whichwill react with the dye intermediate causing a visible colored mark atpoints where the microcapsules have been ruptured and the dyetransferred. Other recent applications in which microcapsules have beenused extensively are in adhesives and adhesive tapes. fertilizers,pharmaceuticals. foods and cosmetics.

A microencapsulation system has been described in copending U.S. patentapplication Ser. No. 174,045 entitled Microencapsulation System" thatwas filed on Aug. 13. 1971 in the name of A. E. Vassiliades, whereinmicrocapsules are formed by providing a crosslinking or complexing agentto an emulsion containing an emulsifying agent which is a preformedpolymer which possesses cross-linkable groups or complexing sites. Thissystem avoided the need for any extraneous hardening agents in order toprovide capsules having a high degree of structural integrity.

Another microencapsulation system has been described in copending U.S.patent application Ser. No. 55.925 entitled "Water-ResistantMicrocapsular Opacifier System and Products" that was filed on July 17.1970 in the name of M. P. Powell, now U.S. Pat. No. 3.779.941. issued onDec. 18, 1973 wherein oilcontaining microcapsules are produced by thereaction of a polymeric. oil-soluble cross-linking agent with apolymeric emulsifying agent. Thus, a thermosetting condensationpolymer-containing oily solution and a thermoplasitc polymer-containingaqueous solution are admixed. and a chemical reaction occurs at theoil/water interface to provide a solid, cross-linked, resinous capsulewall having excellent resistance to water.

1t has now been found that pressure-rupturable, oilcontainingmicrocapsules having good structural integrity may be produced by aprocess which comprises providing an aqueous solution of awater-soluble, polymeric. film-forming, emulsifying agent, whichemulsifier possesses hydroxyl groups, and thereafter forming an emulsionby admixing a water-immiscible, oily material containing an oil-soluble,non-polymeric crosslinking agent for said emulsifying agent selectedfrom the group consisting of polyfunctional isocyanates and orthoestersof Group IV elements. The cross-linking agent interacts with thehydroxyl groups of the polymeric emulsifying agent to form a solid,cross-linked, resinous, capsule wall.

Thus. a process for the formation of pressurerupturable oil-containingmicrocapsules is provided which comprises admixing:

A. a water-immiscible. oily material containing an oil-soluble.non-polymeric cross-linking agent selected from the group consisting ofa polyfunctional isocyanate and an orthoester of a Group N element; and

B. an aqueous solution of an hydroxyl groupeontaining. polymeric,emulsifying agent:

said admixing being conducted under conditions to form an oil-in-vvateremulsion wherein said oily material is dispersed in the form ofmicroscopic emulsion droplets in an aqueous. continuous phase, reactingsaid cross-linking agent with said polymeric emulsifying agent andthereby surrounding each of said droplets with a solid, cross-linkedcapsule wall. said polymeric emulsifying agent being the sole reactantfor said crosslinking agent.

The reaction of the cross-linking agent with the polymeric emulsifyingagent, i.e., the curing step. may be conducted at any suitabletemperature, for example, between about ambient temperature and about100C. for periods of time between about 1 and about 24 hours. The uppertemperature at which the curing step may be conducted is only limited bythe temperature at which the emulsion will break, i.e. the stabilitylimit of the emulsion. Preferably. the cross-linking reaction isconducted at a temperature in the range of between about 40 and aboutC., for a period of about l-3 hours.

The ratio of polymeric emulsifying agent to crosslinking agent that isprovided in the emulsion is at least 1 part by weight of emulsifyingagent per part of crosslinking agent. Thus, suitable ratios ofemulsifier to cross-linking agent include between 1 and about parts byweight of emulsifying agent per part of crosslinking agent, preferablybetween about 4 and about 20 parts by weight of emulsifying agent perpart of crosslinking agent.

The encapsulation system of the present invention offers many distinctadvantages. For example, the present system eliminates the need for aseparate emulsifying agent and a separate co-reactant for thecrosslinking agent. Thus, prior systems, such as those involvinginterfacial polycondensation, have required that separate, monomeric,co-reactants be provided in the discontinuous oil phase and in thecontinuous water phase, respectively, of the emulsion system in additionto an emulsifying agent. On the other hand, the present system employs adual-functional, polymeric emulsifying agent which not only aids in theformation of the emulsion, but is cross-linked at the oil/waterinterface from within the oil droplet by a non-polymeric crosslinkingagent to form the solid, capsule wall. Thus, the addition of a separate,monomeric co-reactant in the continuous phase, such as in priorinterfacial polycondensation processes, is obviated. Other encapsulationsystems have been proposed whereby a cross-linking agent precursor isinitially provided in the waterinsoluble internal phase. However, theprecursor material must be then converted into a water-solublecrosslinking agent in order to react with the polymeric wallformingmaterial. In contradistinction thereto, the cross-linking agent of thepresent invention is oilsoluble and need not be converted to awater-soluble form in order to undergo a cross-linking reaction with thepolymeric emulsifying agent of the present inven' tion. Although it isnot intended to limit this invention by any particular theory ormechanism. it is believed that the polymeric emulsifying agent isadsorbed on the surface of the oil droplet. and the oleophilic portionsof this molecule dip into and penetrate the oil phase. thus carryingwith it a number of adjacent hydroxyl groups. The oil-solublecrosslinking agent reacts with these groups in the oil phase formingcross-links between polymer chains and thereby insolubilize the adsorbedpolymeric layer at the oil droplet/water interface.

This cross-linked polymeric shell. now being insoluble in both the waterand oil phases is immobilized at this interface and no longer canparticipate in adsorption-desorption equilibria. In this way a shell isbuilt around the oil droplet forming the desired microcap sules by areaction taking place on the oil side of the oil/water interface. Thepresent cross-linking agents are highly water sensitive and are veryrapidly rendered inactive if they come into contact with the waterphase.

The polymeric. emulsifier of the present invention is employed as themajor wall former. and is therefore provided to the system in amountsexceeding the usual emulsifying amount" of such material. As will behereinafter discussed. the ratio of wall-forming emulsifier tocross-linking agent is at least one part of emulsifier per part ofcross-linking agent.

Another advantage of the present invention resides in the fact that thecross-linking agent is provided to the emulsion in the oil phase. whichlater forms the core of the microcapsule. Thus, the cross-linking agentis efficiently used and effectively positioned to contribute to theformation of the capsule wall from the inside of the wall. In many priorsystems a co-reactant is provided to the emulsion by means ofthecontinuous phase and becomes dispersed throughout such phase.'Therefore, such co-reactant does not fully contribute to the formationof the capsule wall. since it is at least partially unavailable at theoil/water interface for reaction.

The microcapsules of the present invention are capable of being employedin carbonless copy systems and provide excellent properties thereto. Forexample, the capsules of the present invention are able to retain highlyvolatile oils during exposure of the coated copy paper to severeconditions of temperature. humidity, and the like.

The solid coating or wall of the microcapsules of the present inventionare initially formed around the dispersed oil droplets solely byproviding the oil-soluble cross-linking agent to the emulsion, whichcross-linking agent is dissolved in the oily material that is admixedwith the aqueous continuous phase containing the polymeric emulsifyingagent. The term solely" or sole coreactant" as used herein is intendedto exclude the formation of the solid capsule wall by providing in thecontinuous phase a monomeric co-reactant for the oilsolublecross-linking agent. However, the term solely" as used herein is notintended to exclude, for example, the addition of a second cross-linkingagent for the emulsifying agent.

Also, the use of any material for inducing phase separation is excluded,such as has been the case in prior systems involving coacervation".Thus, the present system is conducted in the absence of coacervationthereby obviating the need for coacervating agents, such as sodiumsulfate or the like to cause a liquidliquid phase separation.

Thus. according to another aspect of the invention, a secondcross-linking agent may be added to the already-formed microcapsulardispersion in order to insure complete insolubilization of thewall-forming emulsifying agent. This permits the utilization ofwatersensitive emulsifying agents, while obviating moisture sensitivityin the final coated paper product. The capsules ofthe present inventionprovide excellent carbonless copy paper having good dimensionalstability, which paper will not have undersirable curl problems and thelike due to moisture.

Suitable oil-soluble polyfunctional isocyanates that may be employed inthe present invention include, for example, 4.4'-diphenylmethanediisocyanate, toluene diisocyanate. hexamethylene diisocyanate,triphenylmethane triisocyanate, mixtures of such isocyanates, andadducts of such isocyanates with polyhydric alcohols, such astrimethylolpropane.

The orthoesters of Group IV elements which may be employed ascross-linking agents include the aliphatic and aromatic orthoesters ofGroup [Va and IV]; ele ments, preferably the lower alkyl and arylorthoesters of Group IV elements, such as tetraethyl orthosilicate,tetrapropyl orthosilicate, tetraphenyl orthosilicate, tetraethyltitanate, tetrapropyl titanate, tetrabutyl titanate. tetraphenyltitanate, tetraethyl germanate, tetrapropyl orthocarbonate. and thelike.

As previously mentioned, the film-forming polymeric emulsifying agent ofthe present invention is an hydroxyl group-containing polymer. Suitablehydroxyl group-containing polymers include polyvinyl alcohol, methylcellulose, starch, and the like.

The polyvinyl alcohol especially preferred in this process are thosegrades known as 88 percent (nominal) hydrolyzed, high molecular weightproducts (e.g., commerically available as Covol 97-40 from CPI orElvanol 50-42 from DuPont). However, any of the available water-solublegrades, either fully or partially hydrolyzed, high or low molecularweight, can be utilized.

Substituted starches are the preferred form of starch for use in thepresent invention and may be provided by any suitable process. Forexample, they may be provided by an etherification of the starch ingranule form under non-gelatinizing conditions with a monofunctionaletherifying agent which provides the starch with ether-linkedhydrophobic groups. Thus, the starch granule will become more oleophilicdue to the presence of a high percentage of hydrophobic groups. Thehydrophobic groups may be, for example, alkyl groups having at leastthree carbon atoms, aralkyl groups containing at least seven carbonatoms, and the like. Thus, the term substituted starch as employedherein refers to a starch that has been rendered more oleophilic due toan increase in hydrophobic groups.

Suitable etherifying agents, which react with ungelatinized granulestarch in alkaline media to produce substituted starch, include alkylhalides containing at least three carbon atoms, for example, alkylchloride or bromide, and three substituted alkyl halides such asmethallyl chloride; aralkyl halides, for example, benzyl chloride orbromide, p-halo benzyl chloride or bromide, or 3-choro propenyl benzene;epoxy reagents, for example, phenyl glycidyl ether and allyl glycidylether.

The etherification reaction is conducted until the starch becomes morehydrophobic and essentially nongelatinizable. Finally. the starch isfragmented and reduced to submicronsized particles by treatment withsteam under pressure. The starch is not swollen or cooked but is reducedto very fine particles which are mainly in the microscopic or colloidalsize range. Such starches are described, for example, in US. Pat. No.3,462,283 to Hjermstad et al. the disclosure of which is herebyincorporated by reference.

The polyfunctional isocyanate or orthoester crosslinking agent isutilized in amounts sufficient to result in the formation ofmicrocapsules. The relative amounts vary with the particular system, andmay be easily determined in each case. However, in contradistinction toprior encapsulation systems, the hydroxyl group-containing polymericemulsifying agent of the present invention is dual functional, andserves not only as emulsifying agent, but preferably provides the majorportion of the capsule shell.

Thus, the polymeric emulsifying agent is provided in relativelysubstantial amounts of, for example, at least 1 part by weight ofemulsifier per part of cross-linking agent. with between about 4 andabout parts emulsitier per part by weight of the oil-solublecross-linking agent being preferred as previously indicated. Anespecially preferred range of cross-linking agent based upon the oil isbetween about 1 and about 40 weight percent of cross-linking agent,preferably between about 2 and about l0 weight percent. Emulsificationmay be conducted at any suitable temperature. For example, temperaturesin the range of between about 20 and about 100C, although temperaturesoutside of this range may also be utilized. Subsequent toemulsification, the microcapsular dispersion may be heated to atemperature, for example, in the range of between about 40 and about80C. for a period of between about 1 and about 4 hours under conditionsof mild agitation in order to accelerate the cross-linking reaction. Thecross-linking reaction may be likewise conducted at ambient temperaturesfor longer periods of time, e.g. 24, while obtaining similar results.

According to another aspect of the invention, a second cross-linkingagent for the polymeric emulsifying agent may be added to themicrocapsular dispersion after formation of the solid, cross-linkedwalls by the reaction between the oil-soluble cross-linking agent withinthe oil droplets and the emulsifying agent. Thus, a second cross-linkingagent, which may be a nonmetallic material, such as a formaldehydecondensation product, e.g., urea-formaldehyde, melamineformaldehyde. oran aldehyde, such as glyoxal, etc., may be added via the aqueous,continuous phase of the dispersion. Suitable amounts of the secondcross-linking agent include the same amounts that are utilized for theoil-soluble cross-linking agent. Exemplary amounts of the secondcross-linking agent include, between about I and about 20 parts ofemulsifier per part of the second cross-linking agent. Thus, the watersensitivity of an emulsifying agent, such as polyvinyl alcohol, may besubstantially improved by the addition of an additional cross-linkingagent to the external phase of the microcapsular dispersion at any timeprior to coating the dispersion on paper.

By water immiscible oily materials" is meant lipophilic materials whichare preferably liquid, such as oils, which will not mix with water andwhich are inert with regard to components of the particular system. Lowmelting fats and waxes may also be used in this invention. However, oilsare the preferred nucleus materials since they do not requiretemperature maintenance. In certain embodiments of this invention, thevapor pressure and viscosity of the oily material are to be considered.For example, in the art of making a transfer sheet record material, alow viscosity-low vapor pressure oil is preferred. The viscosity of theoily medium is a determining factor in the speed with which the markingscan be transferred to the copy sheet since low viscosity oils willtransfer more quickly than oils of higher viscosity. The vapor pressureshould be sufficiently low to avoid substantial losses of the oilthrough evaporation during the encapsulation operation. Suitable oilymaterials which may be employed as the carrier for the cross-linkingagent include the aliphatic and aromatic hydrocarbon oils, such askerosene, mineral spirits, naphtha, xylene, toluene, and the like. Also,for

example, terpenes, such as turpentine; esters, such as dimethylphthalate, dioctyl phthalate, dimethyl azelate, methyl Z-ethylhexanoate,2-ethylhexyl acetate, and the like may be employed.

The amount of emulsifying agent relative to the oily nucleus materialemployed will vary over a wide range depending upon the particularsystem under consideration. However, suitable amounts include betweenabout 5 and about parts of emulsifying agent per 100 parts by weightoil, preferably between about 10 and about 50 parts of emulsifying agentper 100 parts by weight oil.

Within the scope of the present invention, the here indisclosedprocesses may be used to encapsulate an oil alone, or alternatively, theoil may serve merely as a vehicle for carrying another active ingredientor material. In this latter utility, the active material may bedissolved, dispersed or suspended in the oily material. The processes ofthis invention can, therefore, be used to encapsulate medicines,poisons, foods, cosmetics, adhesives or any other material which findsutility in microcapsular form.

In the preferred utility of this invention, viz., transfer sheet recordmaterial, the precess may be used to encapsulate an oily printing ink,such as may be used in smudge-proof typewriter ribbons or carbon papers.In such a use, it has been found expedient to encapsulate a colorless,water-insoluble dye intermediate dissolved in the oil. Colorless dyeintermediates are wholly conventional in such utilities and are wellknown in the art. Exemplary of the colorless dye intermediates whichhave been contemplated for use in this invention are leuco dyes, suchas, crystal violet lactone and derivatives of bis(p-dialkylaminoaryl)methane such as disclosed in US. Pat. Nos. 2,981,733 and 2,981,738.These dye intermediates are colorless in an alkaline or neutral mediumand react to form a visible color in an acidic medium. Thus, when acapsule containing such a compound is ruptured and the compound isdischarged onto an adsorbent, acidic electron-acceptor material, such asa paper web coated with an organic or an inorganic acid material, avisible color appears on the adsorbent material at the point of contact.

Inhibitors may optionally be dispersed in the oily material along withthe dye intermediates. Such materials are helpful in preventing thelight and heat degradation of the intermediates during the encapsulationprocedure, especially when elevated temperatures are required, such aswhen a fat is encapsulated. Inhibitors are also considered to aid in thestabilization of the colored marking on the copy sheet against theeffects of the atmosphere. A small amount (generally about 1 to 10percent by weight of the dye) of an inhibitor. such as N-phenylZ-naphthylamine. may be used in the practice of this invention.

The leuco dye intermediates which are mentioned above are, in general.oil soluble. Oils which are inert with respect to the dye and in whichthe dye has appreciable solubility, e.g. above 0.5 grams of dye per 100grams of oil. are preferable.

Microcapsules having diameters ranging from 0.1 to several hundredmicrons can be produced by the process ofthis invention. However.capsules having diameters in the range of 3.0 to 5.0 microns arepreferred for transfer copy systems.

The emulsion containing the microcapsules may be either coated directlyonto a web material and dried or the microcapsules may be separated fromthe emulsion by some physical means such as filtration orcentrifugation; washed. if desired; redispersed in a solution of abinder; coated onto a web material and dried. Suitable binders includemethyl cellulose, starch, casein, polyvinyl alcohol, polyvinyl acetatelatex, and styrenebutadiene latex. Alternatively, materials such asureaformaldehyde or melamine-formaldehyde condensates may be employed.

The microencapsulated oils ofthis invention are suitable for use in themanufacture of transfer sheet record material. More specifically,capsules containing a leuco dye intermediate in the oil are to be coatedonto one side ofa web material and dried. The coating operation isperformed by conventional means, such as by use of an air knife. Thecapsule coatings are dried at temperatures ranging from about 40 to 75C.At these temperatures. no appreciable degradation of the capsules, andin particular, the leuco dye intermediate, takes place.

The web material commonly used in transfer sheet record material ispaper and is, therefore, preferable in the practice of this invention.However, the microcapsules produced by the herein-disclosed processesare also capable of being coated onto other materials such as plasticand fabric or textile webs, When using a web material having a highdegree of porosity, it is advisable to pre-coat the web with a materialwhich will reduce seepage of the microcapsular coating through the web.Impregnating the web material with polyvinyl alcohol or abutadiene-styrene latex is the conventional practice for producing anessentially impervious substrate.

Transfer sheets made according to the various embodiments of thisinvention have a pleasant appearance and are almost completelysmudge-proof when brought into face-to-face contact with a copy sheetcontaining a coating of an adsorbent electron-acceptor material. Inaddition, they show a marked improvement over the transfer sheetspresently available in commerce. It has been found that coated papercomprising microcapsules which contain a leuco dye intermediatedissolved in the oil and which microcapsules are formed by the processof this invention are extremely stable.

The following examples illustrate the best modes contemplated forcarrying out this invention. All percentages are by weight unlessotherwise specified.

EXAMPLE 1 Six hundred sixty seven grams of a 6 percent by weight aqueoussolution of polyvinyl alcohol (commercially available as Elvanol 50-42from DuPont) are charged to a Waring blender, Meanwhile, an oilcomprising a 50/50 mixture of partially hydrogenated terphenyl andcoconut oil and containing 2.1 percent crystal violet lactone and 1.8percent benzoyl leucomethylene blue is provided with 2 percent by weightof the oil-soluble cross-linking agent, 4,4- diphenylmethanediisocyanate, based upon the oil.

Approximately 93.5 parts by volume of the oil containing the dissolveddiisocyanate are added to the aqueous polyvinyl alcohol solution underconditions of brisk agitation. eg. employing a Waring blender.Emulsification is continued until a particle size of about 3 to 5microns diameter is obtained.

The emulsion is then heated while under mild agitation at a temperatureof C. for between about I and about 4 hours to form microcapsules havingsolid, cross-linked, oil-impermeable capsule walls.

The resulting microcapsular suspension is cooled and a 5 percent aqueoussolution of hydroxyethyl cellulose binder is added. The dispersion isthen coated onto a paper web substrate and dried to provide apressurerupturable transfer sheet.

EXAMPLE 2 One hundred grams of the oily material monoisopropyl biphenyl,containing 2.1 grams of crystal violet lactone and L8 grams of benzoylleucomethylene blue are provided with 3.0 grams of a 3 to 1 molar adductof toluene diisocyanate and trimethylolpropane. The resulting oilysolution is then slowly added to 267 grams of a 15 percent aqueoussolution of polyvinyl alcohol (Elvanol 70-05) under conditions of briskagitation in a Waring blender. Agitation is continued until the emulsionparticles reach an average particle diameter of about 4 to 5 microns.The emulsion is then heated while under mild agitation at a temperatureof 60C. for 2 hours. Discrete microcapsules having a coherent wallstructure are provided.

The resulting dispersion is coated onto a paper web to provide atransfer copy sheet. The paper web is dried at a temperature of about 50to 60C.

EXAMPLE 3 The procedure of Example 2 is repeated with the ex ceptionthat prior to heating the emulsion under conditions of mild agitation, 2grams of melamineformaldehyde condensation product are added to themicrocapsular dispersion in order to further insolubllize the capsulewall from the outside of the capsule.

The resulting microcapsular dispersion is coated onto a paper web anddried to provide a pressure-rupturable transfer sheet as before.

EXAMPLE 4 1a paper substrate to provide a transfer copy sheet as beore.

EXAMPLE One hundred grams of an alkylated, partially hydrogenatednaphthalene oil, containing 2.1 percent by weight crystal violetlactone, 1.8 percent by weight benzoyl leucomethylene blue, and from 1to percent of the 3 to 1 molar reaction product of toluene diisocyanatewith trimethylolpropane, are emulsified in from 200 to 800 grams of a 5percent aqueous solution of a high molecular weight, about 88 percenthydrolyzed, polyvinyl alcohol employing a Waring blender. Emulsiticationis continued until a particle size of about 3 to 5 microns in diameteris obtained.

The emulsion is then heated while under mild agitation at a temperatureof about 60C. fOr about 2 hours.

The resulting microcapsular suspension is cooled and from 1.4 grams to5.7 grams of a 70 percent by weight aqueous solution of amelamine-formaldehyde condensation product, and from 10 grams to 40grams of a 5 percent by weight aqueous solution of carboxymethylcellulose are added. The dispersion is then coated onto a papersubstrate to provide a pressure-rupturable transfer sheet.

Although the invention has been described in considerable detail withparticular reference to certain preferred embodiments thereof,variations and modifications can be effected within the spirit and scopeof the invention as described hereinbefore, and as defined in theappended claims.

We claim:

1. A process for the formation of pressurerupturable. oil-containingmicrocapsules, which comprises admixing:

A. a water-immiscible, oily material containing an oil-soluble.non-polymeric cross-linking agent selected from the group consisting ofa polyfunctional isocyanate and an orthoester of a Group IV element; and

B. an aqueous solution of an (hydroxy-group containing.) organic,polymeric, emulsifying agent, containing a plurality of hydroxyl groups,and selected from the group consisting of polyvinyl alcohol, methylcellulose, starch and benzyl-substituted starch,

said admixing being conducted under conditions to form an oil-in-wateremulsion, wherein said oily material is dispersed in the form ofmicroscopic emulsion droplets in an aqueous, continuous phase, saidemulsifying agent aiding in the formation of said emulsion andpossessing cross-linkable hydroxyl groups capable of reacting with saidcross-linking agent to form a crosslinked capsule wall at the oil/waterinterface, reacting said cross-linking agent with said hydroxyl groupsof said polymeric emulsifying agent and thereby surrounding each of saiddroplets with a solid, cross-linked capsule wall, said polymericemulsifying agent being the sole co-reactant for said oil-solublecross-linking agent.

2. The process of claim 1 wherein said emulsifying agent is employed ina ratio of at least 1 part of said polymeric emulsifying agent per partby weight of said cross-linking agent.

3. The process of claim 2 wherein a ratio of between about 4 and aboutparts by weight of said polymeric emulsifying agent per part ofcross-linking agent is employed.

4. The process of claim 1 wherein said cross-linking agent is apolyfunctional isocyanate.

5. The process of claim 4 wherein said polyfunctional isocyanate is amember selected from the group consisting of 4,4-diphenylmethanediisocyanate, toluene diisocyanate, hexamethylene diisocyanate,triphenylmethane triisocyanate, and adducts thereof with polyhydricalcohols.

6. The process of claim 5 wherein said polyfunctional isocyanate is4,4'-diphenylmethane diisocyanate.

7. The process of claim 5 wherein said polyfunctional isocyanate istoluene diisocyanate.

8. The process of claim 5 wherein said polyfunctional isocyanate is anadduct of toluene diisocyanate and trimethylolpropane.

9. The process of claim 1 wherein said cross-linking agent is anorthoester of a Group IV element.

10. The process of claim 9 wherein said cross-linking agent wherein saidcross-linking agent is either tetraethyl orthosilicate, tetrabutyltitanate or tetrapropyl orthocarbonate.

11. The process of claim 10 wherein said crosslinking agent istetrabutyl titanate.

12. The process of claim 1 wherein said emulsifying agent is a memberselected from the group consisting of polyvinyl alcohol, methylcellulose and starch.

13. The process of claim 8 wherein the emulsifying agent is polyvinylalcohol.

14. The process of claim 1 wherein a second crosslinking agent is addedto an aqueous dispersion of said solid-walled microcapsules.

15. The process of claim 14 wherein said second cross-linking agent is aformaldehyde condensation product.

16. The process of claim 15 wherein said second cross-linking agent ismelamine-formaldehyde.

l7. Pressure-rupturable microcapsules as made according to the processof claim 1.

18. A process for the formation of pressurerupturable, oil-containingmicrocapsules which comprises admixing:

A. A water-immiscible, oily material containing an oil-soluble,non-polymeric polyfunctional isocyanate cross-linking agent and acolorless, waterinsoluble dye intermediate compoundyand B. an aqueoussolution of an organic, polyhydroxyl, polymeric, emulsifying agentselected from the group consisting of polyvinyl alcohol, methylcellulose, starch and benzyl-substituted starch,

said admixing being conducted under conditions to form an oil-in-wateremulsion, wherein said oily material is dispersed in the form ofmicroscopic emulsion droplets in an aqueous, continuous phase, saidemulsifying agent aiding in the formation of said emulsion andpossessing cross-linkable hydroxyl groups capable of reacting with saidcross-linking agent to form a crosslinked capsule wall at the oil/waterinterface, reacting said cross-linking agent with said hydroxyl groupsof said polymeric emulsifying agent and thereby surrounding each of saiddroplets with a solid, cross-linked capsule wall, said polymericemulsifying agent being the sole co-reactant for said oil-solublecross-linking agent.

19. The process of claim 18 wherein said dye intermediate compound iscrystal violet lactone.

1 1 12 20. The process of claim 4 wherein said emulsifying 22. Theprocess of claim 20 wherein the emulsifying agent is a member selectedfrom the group consisting agent is polyvinyl alcohol. of polyvinylalcohol, methyl cellulose and starch. 23. The process of claim 20wherein the emulsifying 21. The process of claim 18 wherein theemulsifying agent is methyl cellulose. agent is a benzyl-substitutedstarch. 5

1. A PROCESS FOR THE FORMATION OF PRESSURE-RUPTURABLE, OILCONTAININGMICROCAPSULES, WHICH COMPRISES ADMIXING: A. A WATER-IMMISCIBLE, OILYMATERIAL CONTAINING AN OILSOLUBLE, NON-POLYMERIC CROSS-LINKING AGENTSELECTED FROM THE GROUP CONSISTING OF A POLYFUNCTIONAL ISOCYANATE AND ANORTHOESTER OF A GROUP IV ELEMENT; AND B. AN AQUEOUS SOLUTION OF AN(HYDROXY-GROUP CONTAINING,) ORGANIC, POLYMIERIC, EMULSIFYING AGENT,CONTAINING A PLURALITY OF HYDROXYL GROUPS, AND SELECTED FROM THE GROUPCONSISTING OF POLYVINYL ALCOHOL, METHYL CELLULOSE, STARCH ANDBENZYL-SUBSTITUTED STARCH, SAID ADMIXING BEING CONDUCTED UNDERCONDITIONS TO FORM AN OIL-IN-WATER EMULSION, WHEREIN SAID OILY MATERIALIS DISPERSED IN THE FORM OF MICROSCOPIC EMULSION DROPLETS IN AN AQUEOUS,CONTINUOUS PHASE, SAID EMULSIFYING AGENT AIDING IN THE FORMATION OF SAIDEMULSION AND POSSESING CROSS-LINKING HYDROXYL GROUPS CAPABLE OF REACTINGWITH SAID CROSS-LINKING AGENT TO FORM A CROSS-LINKED CAPSULE WALL AT THEOIL/WATER INTERFACE, REACTING SAID CROSS-LINKING AGENT WITH SAIDHYDROXYL GROUPS OF SAID POLYMERIC EMULSIFYING AGENT AND THEREBYSURROUNDING EACH OF SAID DROPLETS WITH A SOLID, CROSS-LINKED CAPSULEWALL, SAID POLYMERIC EMULSIFYING AGENT BEING THE SOLE CO-REACTANT FORSAID OIL-SOLUBLE CROSS-LINKING AGENT.
 2. The process of claim 1 whereinsaid emulsifying agent is employed in a ratio of at least 1 part of saidpolymeric emulsifying agent per part by weight of said cross-linkingagent.
 3. The process of claim 2 wherein a ratio of between about 4 andabout 20 parts by weight of said polymeric emulsifying agent per part ofcross-linking agent is employed.
 4. The process of claim 1 wherein saidcross-linking agent is a polyfunctional isocyanate.
 5. The process ofclaim 4 wherein said polyfunctional isocyanate is a member selected fromthe group consisting of 4,4''-diphenylmethane diisocyanate, toluenediisocyanate, hexamethylene diisocyanate, triphenylmethanetriisocyanate, and adducts thereof with polyhydric alcohols.
 6. Theprocess of claim 5 wherein said polyfunctional isocyanate is4,4''-diphenylmethane diisocyanate.
 7. The process of claim 5 whereinsaid polyfunctional isocyanate is toluene diisocyanate.
 8. The processof claim 5 wherein said polyfunctional isocyanate is an adduct oftoluene diisocyanate and trimethylolpropane.
 9. The process of claim 1wherein said cross-linking agent is an orthoester of a Group IV element.10. The process of claim 9 wherein said cross-linking agent wherein saidcross-linking agent is either tetraethyl orthosilicate, tetrabutyltitanate or tetrapropyl orthocarbonate.
 11. The process of claim 10wherein said cross-linking agent is tetrabutyl titanate.
 12. The processof claim 1 wherein said emulsifying agent is a member selected from thegroup consisting of polyvinyl alcohol, methyl cellulose and starch. 13.The process of claim 8 wherein the emulsifying agent is polyvinylalcohol.
 14. The process of claim 1 wherein a second cross-linking agentis added to an aqueous dispersion of said solid-walled microcapsules.15. The process of claim 14 wherein said second cross-linking agent is aformaldehyde condensation product.
 16. The process of claim 15 whereinsaid second cross-linking agent is melamine-formaldehyde. 17.Pressure-rupturable microcapsules as made according to the process ofclaim
 1. 18. A process for the formation of pressure-rupturable,oil-containing microcapsules which comprises admixing: A. Awater-immiscible, oily material containing an oil-soluble, non-polymericpolyfunctional isocyanate cross-linking agent and a colorless,water-insoluble dye intermediate compound; and B. an aqueous solution ofan organic, polyhydroxyl, polymeric, emulsifying agent selected from thegroup consisting of polyvinyl alcohol, methyl cellulose, starch andbenzyl-substituted starch, said admixing being conducted underconditions to form an oil-in-water emulsion, wherein said oily materialis dispersed in the form of microscopic emulsion droplets in an aqueous,continuous phase, said emulsifying agent aiding in the formation of saidemulsion and possessing cross-linkable hydroxyl groups capable ofreacting with said cross-linking agent to form a cross-linked capsulewall at the oil/water interface, reacting said cross-linking agent withsaid hydroxyl groups of said polymeric emulsifying agent and therebysurrounding each of said droplets with a solid, cross-linked capsulewall, said polymeric emulsifying agent being the sole co-reactant forsaid oil-soluble cross-linking agent.
 19. The process of claim 18wherein said dye intermediate compound is crystal violet lactone. 20.The process of claim 4 wherein said emulsifying agent is a memberselected from the group consisting of polyvinyl alcohol, methylcellulose and starch.
 21. The process of claim 18 wherein theemulsifying agent is a benzyl-substituted starch.
 22. The prOcess ofclaim 20 wherein the emulsifying agent is polyvinyl alcohol.
 23. Theprocess of claim 20 wherein the emulsifying agent is methyl cellulose.